EP3526283B1 - Polyamides ignifugés - Google Patents

Polyamides ignifugés Download PDF

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Publication number
EP3526283B1
EP3526283B1 EP17777036.9A EP17777036A EP3526283B1 EP 3526283 B1 EP3526283 B1 EP 3526283B1 EP 17777036 A EP17777036 A EP 17777036A EP 3526283 B1 EP3526283 B1 EP 3526283B1
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weight
thermoplastic molding
component
molding composition
bis
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EP3526283A1 (fr
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Michael Roth
Christoph Minges
Klaus Uske
Michaela HEUßLER
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K2003/343—Peroxyhydrates, peroxyacids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/04—Heat-responsive characteristics

Definitions

  • the invention further relates to the use for producing moldings of any type and moldings obtained from the molding compositions according to the invention.
  • melamine derivatives (melamine cyanurate) as flame retardants for polyamides has been known for many years (see US 3660344 ).
  • Fire-resistant polyamides have recently become increasingly important. There is particular interest in products in light color settings for the electrical sector. Of the known fire protection systems, however, red phosphorus and halogen compounds in combination with synergists are not suitable for this area of application. Halogen compounds reduce the electrical properties such as tracking resistance and dielectric strength. Due to its inherent color, red phosphorus cannot be used for light color settings. For the production of light-colored, unreinforced and flame-retardant polyamides, the DE-A 1694254 the addition of melamine is recommended. In the case of glass fiber reinforced polyamides, melamine and melamine salts such as. B. melamine cyanurate less effective, the glow wire resistance of these products is - especially in thin walls - very low.
  • glass fibers if used, can be used as conventional continuous fibers (rovings) or cut fibers (4-6 mm long fiber bundles). Shear in the extruder then results in a glass fiber length distribution in the product which, with normal processing, is around 250-300 ⁇ m (based on a product with 25% glass fiber content). It must be taken into account that the average fiber length generally decreases with increasing fiber content, since there is increased fiber interactions in the incorporation zone and thus increased fiber breakage ( F. Jardinsteiner, R. Theysohn, Comp. Sci. Techn. 23 (1985) 231 ).
  • DE 699 12 241 T2 relates to flame retardant polyamide compositions.
  • the compositions contain a derivative of melamine and calcined kaolin as a flame retardant system.
  • the calcined kaolins are obtained from hydrated aluminosilicates (kaolinite) by hot dehydration, see paragraph [0011].
  • molding compounds are used in which the polyamide is largely based on polyhexamethylene adipamide (PA 6.6).
  • Polycaprolactam (PA 6) is mixed with the polyhexamethylene adipamide in a maximum amount of 10% or used as a copolymer with it, see polyamides A 2 and A 3 in the example.
  • EP-A-1 762 592 relates to polymeric molding compounds based on thermoplastic polyamides.
  • the molding compositions can contain fillers.
  • Preferred fillers include amorphous silicic acid and kaolin, in addition to other fillers.
  • Talc is used in the examples, sometimes combined with glass fibers, see components E / 1, E / 2 and D.
  • the molding compositions have phosphinic acid salts or diphosphinic acid salts as a further essential ingredient.
  • fibrous reinforcing materials must necessarily be present in addition to the filler.
  • thermoplastic molding compositions which have good mechanical properties and good flame retardancy.
  • mineral fillers should enable flame retardancy, resulting in the shortest possible afterburning times in the glow wire test.
  • a naturally occurring mineral filler which consists of a mixture of corpuscular, (crypto) crystalline and amorphous silica and calcined lamellar kaolin (Neuburg Siliceous Earth).
  • the mineral mixture is a loose, crystalline heap that cannot be separated by physical methods.
  • the silica portion has a round grain shape and consists of aggregated cryptocrystalline primary particles approx. 200 nm in size, which are coated with amorphous silica like an opal. This structure results in the relatively high specific surface and oil number.
  • thermoplastic molding compositions according to the invention are described below.
  • the molding compositions according to the invention contain, as component A), from 30 to 97, preferably from 40 to 92 and in particular from 40 to 80% by weight of at least one polyamide, with partially crystalline polyamides being preferred.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 79.9 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C according to ISO 307.
  • Semicrystalline or amorphous resins with a molecular weight (weight average) of at least 5,000 are preferred.
  • polyamides derived from lactams with 7 to 13 ring members such as polycaprolactam, polycapryllactam and polylaurolactam, and polyamides obtained by reacting dicarboxylic acids with diamines.
  • Alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned here as acids.
  • Particularly suitable diamines are alkanediamines with 6 to 12, in particular 6 to 8 carbon atoms and m-xylylenediamine (e.g. Ultramid® X17 from BASF SE, a 1: 1 molar ratio of MXDA to adipic acid), di- (4-aminophenyl) methane, Di- (4-amino-cyclohexyl) -methane, 2,2-di- (4-aminophenyl) -propane, 2,2-di- (4-aminocyclohexyl) -propane or 1,5-diamino-2-methyl- pentane.
  • m-xylylenediamine e.g. Ultramid® X17 from BASF SE, a 1: 1 molar ratio of MXDA to adipic acid
  • di- (4-aminophenyl) methane Di- (4-amino-cyclohexyl) -methane
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units (e.g. Ultramid® C31 from BASF SE).
  • Ultramid® C31 from BASF SE
  • polyamides are obtainable from ⁇ -aminoalkylnitriles such as aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by what is known as direct polymerization in the presence of water, such as in the DE-A 10313681 , EP-A 1198491 and EP 922065 described.
  • PA 6 aminocapronitrile
  • PA 66 adiponitrile with hexamethylenediamine
  • PA 6 adiponitrile with hexamethylenediamine
  • polyamides obtainable by copolymerizing two or more of the aforementioned monomers or mixtures of several polyamides are suitable, the mixing ratio being as desired. Mixtures of polyamide 66 with other polyamides, especially copolyamides 6/66, are particularly preferred.
  • partially aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous whose triamine content is less than 0.5, preferably less than 0.3% by weight (see EP-A 299 444 ).
  • Other high-temperature resistant polyamides are from the EP-A 19 94 075 known (PA 6T / 6I / MXD6). Such polyamides are used in particular in amounts of up to 20, preferably up to 10% by weight, based on 100% A), with partially crystalline polyamides.
  • the preparation of the preferred partially aromatic copolyamides with a low triamine content can be carried out according to the EP-A 129 195 and 129 196 procedures described.
  • the molding compositions according to the invention contain as component B) 1 to 20, preferably 2 to 15 and in particular 2 to 13% by weight of a melamine compound.
  • the melamine cyanurate which is preferred according to the invention (component B) is a reaction product of preferably equimolar amounts of melamine (formula I) and cyanuric acid or isocyanuric acid (formulas Ia and Ib)
  • the commercially available product is a white powder with an average grain size d 50 of 1.5 - 7 ⁇ m and ad 99 value less than 50 ⁇ m.
  • melamine sulfate melamine
  • melamine borate oxalate
  • phosphate primary phosphate secondary and pyrophosphate secondary
  • neopentyl glycol boric acid melamine and polymeric melamine phosphate ( CAS # 56386-64-2 or 218768-84-4).
  • the particle size distribution is usually determined by laser diffraction (analogous to ISO 13320).
  • the molding compositions according to the invention contain 1 to 50, preferably 5 to 45 and in particular 10 to 40% by weight of a mineral filler composed of a mixture of essentially (crypto) crystalline (C1) and amorphous silica (C2) and calcined Kaolin (C3).
  • a mineral filler composed of a mixture of essentially (crypto) crystalline (C1) and amorphous silica (C2) and calcined Kaolin (C3).
  • a naturally occurring mineral filler which consists of a mixture of corpuscular, (crypto) crystalline and amorphous silica and lamellar kaolin (Neuburg Siliceous Earth).
  • the mineral mixture is a loose, crystalline heap that cannot be separated by physical methods, but can be determined using X-ray diffraction analysis.
  • the silica portion has a round grain shape and consists of aggregated cryptocrystalline primary particles approx. 200 nm in size, which are coated with amorphous silica like an opal.
  • the kaolin content in this mineral filler is calcined by a subsequent thermal treatment and is commercially available as such a mixture.
  • the mineral filler C) contains a mixture of 45 to 70, preferably 53 to 65% by weight C1 with 5 to 15, preferably 7 to 12% by weight C2 and 20 to 40, preferably 25 to 35% by weight C3 , based on 100% C.
  • component C has an Al content of less than 15%, preferably 2 to 10 and in particular 3 to 8% by weight, based on 100% C).
  • component C) has an Si content greater than 30, preferably 35 to 50 and in particular 38 to 45% by weight, based on 100% C).
  • Both the Si and the Al content can be determined using XRF (X-ray fluorescence analysis) in accordance with DIN 51001.
  • Preferred components C) have a specific BET surface area according to DIN ISO 9277 of 5 to 15, preferably 6 to 10, m 2 / g.
  • Preferred components C) have an oil number according to DIN ISO 787 Part 5 of 50 to 60, preferably 52 to 58 g / 100 g.
  • the surface of the mineral filler C) can be pretreated for better compatibility with the polymer matrix.
  • component D For detailed information, reference is made to component D).
  • Fibrous fillers D include carbon fibers, glass fibers, glass spheres, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are available in amounts from 0 to 20, preferably from 0.5 to 20 , in particular from 5 to 20% by weight can be used.
  • Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, glass fibers being particularly preferred as E-glass. These can be used as rovings or chopped glass in standard shapes.
  • the fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastics.
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as the X substituent.
  • the silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1.0 and in particular 0.05 to 0.5% by weight (based on D) for surface coating.
  • Needle-shaped mineral fillers are also suitable.
  • acicular mineral fillers are understood to mean a mineral filler with a strongly pronounced acicular character. Needle-shaped wollastonite is an example.
  • the mineral has an L / D (length diameter) ratio from 8: 1 to 35: 1, preferably from 8: 1 to 11: 1.
  • the mineral filler can optionally have been pretreated with the abovementioned silane compounds; however, pre-treatment is not absolutely necessary.
  • the polyamide molding compositions according to the invention can contain a fibrous filler with an average arithmetic fiber length of 70 to 200 ⁇ m, preferably 80 to 180 ⁇ m and in particular 100 to 150 ⁇ m.
  • the mean diameter is generally from 3 to 30 ⁇ m or mm, preferably from 8 to 20 ⁇ m or mm and in particular from 10 to 14 ⁇ m or mm.
  • the desired fiber length can e.g. be adjusted by grinding in a ball mill, whereby a fiber length distribution results.
  • the average fiber length is ⁇ 200 ⁇ m, the reduction in the fiber length leads to a free-flowing bulk material that can be mixed into the polymer like a powder. Due to the short fiber length, only a slight further shortening of the fiber length occurs during incorporation.
  • the fiber content is usually determined after incinerating the polymer.
  • the ash residue is generally taken up in silicone oil and photographed at 20 times magnification using the microscope.
  • the length of at least 500 fibers can be measured on the images and the (arithmetic) mean value (d 50 ) calculated from this.
  • the d 50 value is preferably less than or equal to 180, preferably less than or equal to 160 and in particular less than or equal to 150 ⁇ m.
  • the d 10 and d 90 values of the glass fiber length distribution can also be determined.
  • the d 10 value here means that 10% of the glass fibers in the sample have a length x.
  • d 10 values less than or equal to 60 ⁇ m, preferably less than or equal to 55 ⁇ m, and d 90 values less than or equal to 350 ⁇ m, preferably less than or equal to 290 ⁇ m, have proven to be advantageous.
  • the molding compositions according to the invention contain 0 to 25% by weight of talc as component E). If used, this is preferably used in amounts of 5 to 20% by weight, in particular 10 to 20% by weight.
  • Talc is a hydrated magnesium silicate with the composition Mg 3 [(OH) 2 / Si 4 O 10 ] or 3 MgOx4SiO 2 xH 2 O. These so-called three-layer phyllosilicates have a triclinic, monoclinic or rhombic crystal structure with a flaky appearance. Other trace elements Mn, Ti, Cr, Ni, Na, and K can be present, whereby the OH group can be replaced by fluoride.
  • talc whose particle size is 100% less than 20 ⁇ m.
  • the particle size distribution is usually determined by sedimentation analysis and is preferably ⁇ 20 ⁇ m: 100% by weight, ⁇ 10 ⁇ m: 99% by weight, ⁇ 5 ⁇ m: 85% by weight, ⁇ 3 ⁇ m: 60% by weight, ⁇ 2 ⁇ m: 43% by weight.
  • Such products are available as Micro-Talc I.T. available in stores.
  • thermoplastic molding compositions according to the invention can be used as component F) from 0 to 2, preferably from 0.01 to 2% by weight, preferably from 0.05 to 1.5% by weight, particularly preferably from 0.1 to 1.5% by weight contain at least one heat stabilizer.
  • stabilizers based on secondary aromatic amines that can be used according to the invention are adducts of phenylenediamine with acetone (Naugard A), adducts of phenylenediamine with linoles, Naugard 445 (II), N, N'-dinaphthyl-p-phenylenediamine (III), N -Phenyl-N'-cyclohexyl-p-phenylenediamine (IV) or mixtures of two or more thereof
  • Preferred examples of stabilizers based on sterically hindered phenols which can be used according to the invention are N, N'-hexamethylene-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionamide (V), bis- (3.3 -bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid) -glycol ester (VI), 2,1'-thioethylbis- (3- (3,5-di.tert-butyl-4-hydroxyphenyl) propionate (VII), 4-4'-butylidene-bis- (3-methyl-6-tert-butylphenol) (VIII), triethylene glycol 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (IX) or mixtures of two or more thereof
  • thermoplastic molding compositions according to the invention can contain 0 to 1.5% by weight, preferably 0.05 to 1.5% by weight, particularly preferably 0.1 to 1% by weight, of a mold release agent.
  • Mold release agents are added to the molding compound in order to facilitate the demolding of the manufactured product, ie the detachment of the molded part from the mold.
  • the mold release agents are selected from the group consisting of fatty acids and their alkali or alkaline earth or zinc salts, diamides from alkylenediamine and fatty acids. Mold release agents selected from the group consisting of calcium montanate, stearic acid, behenic acid, stearyl alcohol, stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids such as stearin, calcium or zinc stearate are particularly preferred.
  • thermoplastic molding compositions according to the invention can contain 0 to 40% by weight, preferably 0 to 30% by weight, of further additives F) (also called additives).
  • thermoplastic molding compositions containing polyamides or copolyamides can be used as additives. These are preferably selected from the group consisting of pigments, impact modifiers, nucleating agents and mixtures thereof.
  • thermoplastics are generally known, see e.g. R. Gumbleter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser-Verlag, 1983, pages 494 to 510 .
  • the first preferred group of pigments are white pigments such as zinc oxide, white lead (2 PbCO 3 Pb (OH) 2 ), lithopone, antimony white and titanium dioxide.
  • white pigments such as zinc oxide, white lead (2 PbCO 3 Pb (OH) 2 ), lithopone, antimony white and titanium dioxide.
  • rutile and anatase type the two most common crystal modifications (rutile and anatase type) of titanium dioxide, the rutile form in particular is used to color the molding compositions according to the invention white.
  • Black color pigments that can be used according to the invention are iron oxide black (Fe 3 O 4 ), spinel black (Cu (Cr, Fe) 2 O 4 ), manganese black (mixture of manganese dioxide, silicon dioxide and iron oxide), cobalt black and antimony black and particularly preferably carbon black, which is mostly used in the form of furnace or gas black.
  • iron oxide black Fe 3 O 4
  • spinel black Cu (Cr, Fe) 2 O 4
  • manganese black mixture of manganese dioxide, silicon dioxide and iron oxide
  • cobalt black and antimony black and particularly preferably carbon black
  • carbon black which is mostly used in the form of furnace or gas black.
  • inorganic colored pigments such as chromium oxide green or organic colored pigments such as azo pigments and phthalocyanines can be used according to the invention to establish certain color shades. Pigments of this type are common in commerce.
  • pigments or dyes mentioned in mixtures for example carbon black with copper phthalocyanines, since the color dispersion in the thermoplastic is generally facilitated.
  • nigrosine can also be used for blackening.
  • thermoplastic molding compositions according to the invention can be produced by known processes by mixing the starting components A) to C) and, if appropriate, D) to F) in conventional mixing devices and then extruding them. Suitable processing machines are in Handbuch der Kunststoffextrusion, Vol. 1 Basics, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN: 3-446-14339-4 ( Vol. 2 extrusion lines 1986, ISBN 3-446-14329-7 ) described. After the extrusion, the extrudate can be cooled and shredded. Individual components can also be premixed and then the remaining starting materials can be added individually and / or also mixed - also as a concentrate in a carrier polymer (masterbatch). The mixing temperatures are usually 230 to 320 ° C.
  • thermoplastic molding compositions according to the invention are distinguished by good mechanics and HDT and a good flame retardancy rating in accordance with UL 94, which is highly reproducible, and very good glow wire resistance (short afterburning times).
  • thermoplastic molding compounds can be used, for example, in motor vehicle, electrical, electronics, telecommunications, information technology, entertainment, computer industries, in vehicles and other means of transport, in ships, spaceships, in the household, in office equipment, Sports, in medicine and in general in objects and parts of buildings that require increased fire protection.
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • Calcined mineral filler which consists of a mixture of amorphous (10 wt .-%) and crystalline silica (60 wt .-%) and calcined lamellar kaolin (30 wt .-%) according to X-ray diffraction analysis with Rietveld evaluation. (SILFIT ® Z91 from Hoffmann Mineral)
  • Calcined mineral filler which consists of a mixture of amorphous (10 wt .-%) and crystalline silica (60 wt .-%) and calcined lamellar kaolin (30 wt .-%) according to X-ray diffraction analysis with Rietveld evaluation.
  • talc (Grade HP 325 from Pechel GmbH) with a content of 60-62% by weight silicon dioxide, 30-32% by weight magnesium oxide and an average particle size d 50 of 10-14 ⁇ m
  • Short glass fiber, medium length (d 50 ) ⁇ 210 ⁇ m, D 10 ⁇ m
  • Components F 0.3% by weight of 3,3'-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide ( CAS-No. 23128-74-7 ), 0.3 wt .-% aluminum stearate ( CAS-No. 300-92-5 ), and 2.5 wt .-% titanium dioxide ( CAS-No. 13463-67-7 ) used.
  • test specimens for the tests listed in Table 1 were injected on an Arburg 420C injection molding machine at a melt temperature of approx. 250-290 ° C and a mold temperature of approx. 80 ° C.
  • the flame retardancy of the molding compounds was determined using the UL94V method ( Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pp. 14 to 18, Northbrook 1998 ) certainly.
  • the glow wire resistance was determined in accordance with the glow wire inflammability test GWFI (Glow Wire Flammability Index) according to DIN EN 60695-2-12.
  • GWFI Low Wire Flammability Index
  • the maximum temperature was determined on 3 test specimens (for example on plates with a geometry of 60 x 60 x 1.0 mm or a round disk) with the help of a glowing wire at temperatures between 550 and 960 ° C, in 3 successive tests did not lead to ignition even during the exposure time of the glow wire.
  • the test specimen was pressed against a heated glow wire for 30 seconds with a force of 1 Newton.
  • the penetration depth of the glow wire was limited to 7 mm. The test is passed if the test specimen burns for less than 30 seconds after removing the glow wire and if a tissue paper lying under the test specimen does not ignite.
  • Table 1 The sum of the proportions of components A) to F) in Table 1 add up to 100% by weight.
  • Table 1 Component / test method 1 2 3 4th 5 6th 7th 8th 9 10 11 12 13 14th A. 63.9 70.9 68.9 66.9 65.9 62.9 60.9 58.9 55.9 63.9 63.9 60.9 60.9 60.9 B.
  • compositions according to the invention show very good values both with regard to flame retardancy and glow wire resistance (UL94 V-2 and GWFI 960 ° C. at 1.0 mm) and with regard to mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (8)

  1. Masses à mouler thermoplastiques, contenant
    A) 30 à 97 % en poids d'au moins un polyamide,
    B) 1 à 20 % en poids d'un composé de type mélamine,
    C) 1 à 50 % en poids d'une charge minérale construite à partir d'un mélange composé essentiellement de silice (crypto)cristalline (C1) et de silice amorphe (C2) et de kaolin calciné (C3),
    D) 0 à 20 % en poids d'une charge fibreuse,
    E) G à 25 % en poids de talc,
    F) 0 à 15 % en poids d'autres additifs,
    contenant en tant que charge minérale C) un mélange composé de 45 % à 70 % en poids de C1 avec 5 à 15 % en poids de C2 et 20 à 40 % en poids de C3, par rapport à 100 % de C, le composant C) présentant une teneur en Al inférieure à 15 % en poids, et une teneur en Si supérieure à 30 % en poids, par rapport à 100 % de C, et la somme des pourcentages en poids de A) à F) étant de 100 %.
  2. Masses à mouler thermoplastiques selon la revendication 1, dans lesquelles le composant B) est construit à partir de cyanurate de mélamine.
  3. Masses à mouler thermoplastiques selon la revendication 1 ou 2, contenant
    A) 30 à 97 % en poids
    B) 1 à 20 % en poids
    C) 1 à 50 % en poids
    D) 0,5 % à 20 % en poids
    E) 0 à 25 % en poids
    F) 0 à 15 % en poids.
  4. Masses à mouler thermoplastiques selon les revendications 1 à 4, le composant C) présentant une surface spécifique BET selon la norme DIN ISO 9277 de 5 à 15 m2/g.
  5. Masses à mouler thermoplastiques selon la revendication 4, le composant C) présentant un indice d'huile selon la norme DIN ISO 787 Partie 5 de 50 à 60 g/100 g.
  6. Masses à mouler thermoplastiques selon l'une quelconque des revendications 1 à 5, dans lesquelles le stabilisant à la chaleur F) est choisi dans le groupe constitué par des composés monovalents et divalents du cuivre, des stabilisants à base d'amines aromatiques secondaires, des stabilisants à base de phénols stériquement encombrés et leurs mélanges.
  7. Utilisation des masses à mouler thermoplastiques selon l'une quelconque des revendications 1 à 6 pour la préparation de fibres, de feuilles, de corps moulés.
  8. Corps moulé de toute sorte, pouvant être obtenu à partir des masses à mouler thermoplastiques selon les revendications 1 à 6.
EP17777036.9A 2016-10-13 2017-09-28 Polyamides ignifugés Active EP3526283B1 (fr)

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PCT/EP2017/074636 WO2018069055A1 (fr) 2016-10-13 2017-09-28 Polyamides ignifugés

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JP (1) JP7026680B2 (fr)
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018158224A1 (fr) 2017-03-01 2018-09-07 Basf Se Polyamides ignifugés avec pvp
US11859068B2 (en) 2017-06-22 2024-01-02 Basf Se Polyamides with phosphorous and al-phosphonates
ES2936515T3 (es) 2017-10-04 2023-03-17 Basf Se Polvo de sinterización que contiene un agente ignífugo mineral para la fabricación de cuerpos de moldeo
FR3116282B1 (fr) * 2020-11-16 2023-07-28 Arkema France Compositions transparentes avec bonne resistance a l’alcool et tenue a la fatigue
CN112646365B (zh) * 2020-12-19 2022-03-29 杭州本松新材料技术股份有限公司 一种低压电器用导热、阻燃聚酰胺组合物及其应用
EP4105252A1 (fr) 2021-06-17 2022-12-21 Covestro Deutschland AG Matière de moulage thermoplastique à haute propriété ignifuge
CN114517012B (zh) * 2022-03-14 2023-06-06 金旸（厦门）新材料科技有限公司 一种高外观抗菌无卤阻燃聚酰胺复合材料及其制备方法

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2071250A (en) 1931-07-03 1937-02-16 Du Pont Linear condensation polymers
US2071251A (en) 1931-07-03 1937-02-16 Du Pont Fiber and method of producing it
US2130523A (en) 1935-01-02 1938-09-20 Du Pont Linear polyamides and their production
US2130948A (en) 1937-04-09 1938-09-20 Du Pont Synthetic fiber
US2241322A (en) 1938-09-30 1941-05-06 Du Pont Process for preparing polyamides from cyclic amides
US2312966A (en) 1940-04-01 1943-03-02 Du Pont Polymeric material
US2512606A (en) 1945-09-12 1950-06-27 Du Pont Polyamides and method for obtaining same
IL24111A (en) 1964-08-24 1969-02-27 Du Pont Linear polyamides
DE1694254C3 (de) 1968-03-16 1984-06-28 Bayer Ag, 5090 Leverkusen Selbstverlöschende faserverstärkte Polyamid-Formmassen
NL8001764A (nl) 1980-03-26 1981-10-16 Stamicarbon Bereiding van hoogmoleculair polytramethyleenadipamide.
NL8001762A (nl) 1980-03-26 1981-10-16 Stamicarbon Bereiding van voorwerpen op de basis van polyamide.
NL8001763A (nl) 1980-03-26 1981-10-16 Stamicarbon Bereiding van polytetramethyleenadipamide.
DE3321579A1 (de) 1983-06-15 1984-12-20 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen herstellung von polyamiden
DE3321581A1 (de) 1983-06-15 1984-12-20 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen herstellung von polyamiden
DE3609341A1 (de) 1986-03-20 1987-09-24 Bayer Ag Flammfeste, glasfaserverstaerkte polyamidformmassen
DE3889787D1 (de) 1987-07-17 1994-07-07 Basf Ag Teilaromatische Copolyamide mit verringertem Triamingehalt.
DE4307682A1 (de) * 1993-03-11 1994-09-15 Basf Ag Halogenfreie flammgeschützte thermoplastische Polyamidformmassen
DE19532720A1 (de) 1995-09-05 1997-03-06 Basf Ag Flammgeschützte thermoplastische Formmassen
US6194538B1 (en) 1996-08-30 2001-02-27 Basf Aktiengesellschaft Process for producing polyamides from aminonitriles
FR2774689B1 (fr) * 1998-02-11 2001-05-04 Nyltech Italia Composition polyamide ignifugee
DE19935398A1 (de) 1999-07-30 2001-02-01 Basf Ag Verfahren zur Herstellung von Polyamiden aus Dinitrilen und Diaminen
DE10137930A1 (de) 2001-08-07 2003-02-20 Basf Ag Halogenfreie flammgeschützte Polyester
FR2843593B1 (fr) 2002-08-13 2007-04-13 Rhodia Eng Plastics Srl Composition polyamide branche ignifugee
DE10313681A1 (de) 2003-03-26 2004-10-07 Basf Ag Verfahren zur Herstellung von Polyamiden
US7482420B2 (en) 2004-03-24 2009-01-27 Construction Research & Technology Gmbh Silane-terminated polyurethanes with high strength and high elongation
DE102005041966A1 (de) 2005-09-03 2007-03-08 Clariant Produkte (Deutschland) Gmbh Polymere Formmassen auf Basis von thermoplastischen Polyamiden
PL1994075T3 (pl) 2006-03-08 2010-02-26 Basf Se Częściowo aromatyczne kopoliamidy o wysokiej krystaliczności
RU2566148C2 (ru) 2010-03-09 2015-10-20 Басф Се Полиамиды, устойчивые к тепловому старению
US20130338264A1 (en) * 2011-03-11 2013-12-19 Basf Se Condensation products of melamine and phenylphosphonic acid and their use as flame retardants
CN103013110B (zh) 2011-09-27 2014-12-17 台光电子材料股份有限公司 无卤素树脂组成物及应用其的铜箔基板及印刷电路板
CN103214825B (zh) 2013-04-01 2015-09-23 金发科技股份有限公司 阻燃性聚酰胺树脂组合物、制备方法及由其制得的制品
DE102015209451A1 (de) * 2014-06-03 2015-12-03 Basf Se Flammgeschützte Polyamide
DE202014008607U1 (de) 2014-10-31 2014-11-24 Lanxess Deutschland Gmbh Polyamidzusammensetzungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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KR20190069487A (ko) 2019-06-19
CN109844001A (zh) 2019-06-04
US20200048434A1 (en) 2020-02-13
JP2019532155A (ja) 2019-11-07
EP3526283A1 (fr) 2019-08-21
BR112019006385B1 (pt) 2023-03-28
CN109844001B (zh) 2022-03-11
WO2018069055A1 (fr) 2018-04-19
KR102491411B1 (ko) 2023-01-20
JP7026680B2 (ja) 2022-02-28
US11787920B2 (en) 2023-10-17
BR112019006385A2 (pt) 2019-06-25

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